Organic compositions



This invention relates to improved organic compositions and, in one of its aspects, relates more particularly to improved organic compositions in the form of liquid deterioration by corrosion or oxidation.

and solidhydrocarbons that are normally susceptible to Still more particularly, in this aspect,.the invention relates to improved organic compositionsin the form of petroleum distillate hydrocarbon fuels, lubricating oils and greases which, in

P theirI-uninhibited state, tend to react with and corrode metal; surfaces with which they may come into contact inperforming their intended functions.

It is ,well-known that certain types of organic compounds arenorrnally susceptible to deterioration by oxidation or by corrosion when coming into contact with various metalsurfacest For example, it is known that liquid hydrocarbons; in the form of fuel oils or lubricating oils tend to. accumulate considerable quantities of water when maintained for long periods of time in storage vessels;

and when subsequently brought into contact with metal equipment as a result of corrosion, occurs.

surfacesin their functional environments, deterioration of In addition,

where such lubricating oils or other corrosion-inducing materials areincorporated into solid lubricants as in the flformxof. greases, similar deleterious results are encoun- M if tered, thus clearly indicating the necessity for incorporat- 1 ing into such. organic compositions an effective antioxidam and rust-inhibiting agent.

Accordingly, it is an object of this invention to provide Q organic compositions having improved antioxidant and anticor-rosion properties;

Another object of the invention is to provide improved organic compositions in the form of liquid and solid hydroj carbons containing an additive which is adapted to prevent1-corrosion and oxidative deterioration of metallic surfaces.

Still another object of the invention is to provide an effective antioxidant and corrosion inhibiting agent, and t a method for itsmanufacture, for incorporation into the aforementioned organic compositions.

Other objects and advantages inherent in the invention 1 i will become apparent to those. skilled in the art from the following more detailed description.

Itlihas now been found that the aforementioned oxidafive: and corrosive properties of organic compositions, par- I ticularly in the form of fuels and lubricants, can be effectively overcome :by incorporating therein, as an antioxidahtwandanticorrosion agent, small amounts of a metal salt ofa salicylaldimine amide acid having the formula:

Iwherein X is selected from the group consisting of CH: CH, CH CHg and C H CHCH R is an alkyl group having from about8 to about 18 carbon atoms and M is r a divalent metal.

In general; the present invention, in its preferred applications contemplates organic compositions which are normally susceptible to oxidative and corrosive deterioration,

containing a small amount ofthe aforementioned metal UnitedStates Patent 3,296,130 Patented Jan. 3, 1967 salt, usually from about .001 to about 10 percent, by weight, of the total of such compositions. When this metal salt is incorporated into liquid hydrocarbon compositions, such as jet fuels, turbine fuels, gasolines and the like, or in lubricating oils, it is preferably employed in an amount from about .001 to about .01 percent, by weight, of the total composition. When the metal salt is incorporated into a hydrocarbon grease composition, it is preferably employed in an amount from about 0.1 to about 5 percent, by weight, of the total grease.

The organic compounds improved in accordance with the present invention may comprise any materials that are normally susceptible to deterioration b oxidation or corrosion, in the manner previously described. A field of specific applicability is the improvement of liquid hydrocarbons in accordance with the present invention, boiling from about F. to about 750 F. Of particular significance is the treatment of petroleum distillate fuel oils having an initial boiling point from about 75 F. to about 135 F. and an end boiling point from about 250 F. to about 750 F. It should be noted, in this respect, that the term distillate fuel oils is not intended to be restricted to straight-run distillate fractions. These distillate fuel oils can be straight-run distillate fuel oils, catalytically or thermally cracked (including hydrocracked) distillate fuel oils, or mixtures of straight-run distillate fuel oils, naphthas and the like, with cracked distillate stocks. Moreover, such fuel oils can be treated in accordance with wellknown commercial methods, such as acid or caustic treatment, hydrogenation, solvent-refining, clay treatment, and the like.

The distillate fuel oils are characterized by their relatively low viscosity, pour point and the like. The principal property which characterizes these contemplated hydrocarbons, however, is their distillation range. As hereinbefore indicated, this range will lie between about 75 F. and about 750 F. Obviously, the distillation range of each individual fuel oil will cover a narrower boiling range, falling, nevertheless, within the above-specified limits. Likewise, each. fuel oil will boil substantially, continuously, throughout its distillation range.

Particularly contemplated among the fuel oils are Nos. 1, 2 and 3 fuel oils, used in heating and as diesel fuel oils, gasoline and the jet combustion fuels, 'as previously indicated. The domestic fuel oils generally conform to the specifications set forth in ASTM Specification D396- 48T. Specifications for diesel fuels are defined in ASTM Specification D975-48T. Typical jet fuels are defined in Military Specification MILF5624B. In addition, as previously indicated, hydrocarbon lubricating oils of varying viscosity and pour points, failing both within and outside the indicated ranges for the aforementioned fuel oils, may also be effectively treated through the use of the aforementioned metal salts, as antioxidation and anticorrosi-on agents.

As previously indicated, the aforementioned metal salts may also be incorporated, as anti-corrosion agents, in grease composition. Such greases, may comprise a combination of a wide variety of lubricating vehicles and thickening or gelling agents. Thus, greases in which the aforementioned metal salts are particularly effective, may comprise any of the conventional hydrocarbon oils of lubricating viscosity, as the oil vehicle, and may include mineral or synthetic lubricating oils, aliphatic phosphates, esters and di-esters, silicates, siloxanes and oxalkyl ethers and esters. Mineral lubricating oils, employed as the lubricating vehicle, may be of any suitable lubricating viscosity range from about 45 SSU at F. to about 6,000 SSU at 100 F., and, preferably, from about 50 to about 250 SU at 210 F. These oils may have viscosity indexes varying from below 0 to about 100 or higher. Viscosity indexes from about 70 to about 95 are preferred. The average molecular weights of these oils may range from about 250 to about 800. The lubricating oil is employed in the grease composition in an amount sufiicient to constitute the balance of the total grease composition, after accounting for the desired quantity of the thickening agent, and other additive components to be included in the grease formulation.

As previously indicated, the oil vehicles employed in the novel grease formulations of the present invention, in which the aforementioned metal salts 'are incorporated as antiox-idative or anti-corrosion agents, may comprise mineral or synthetic oils of lubricating viscosity. When high temperature stability is not a requirement of the finished grease, mineral oils having 'a viscosity of at least 40 SSU at 100 F., and particularly those falling within the range from about 60 SSU to about 6,000 SSU at 100 F., may be employed. In instances, where synthetic vehicles are employed rather than mineral oils, or in combination therewith, as the lubricating vehicle, various compounds of this type may be successfully utilized. Typical synthetic vehicles include: polypropylene, polypropylene glycol, trimethylol propane esters, neopentyl and pentaerythritol esters, di-(Z-ethyl hexyl) sebacate, di-(Z-ethyl hexyl) adipate, dibutyl phthal'ate, fluorocarbons, silicate esters, silanes, esters of phosphorus-containing acids liquid ureas, ferrocene derivatives, hydrogenated mineral oils, chain-type polyphenyls, siloxanes and silicones (poly-siloxanes), alkyl-substituted diphenyl ethers typified by a butyl-subst-ituted bis (p-phenoxy phenyl) ether, phenoxy phenyl ethers, etc.

The lubricating vehicles of the aforementioned improved greases of the present invention containing the above-described metal salts as additives, are combined with a grease forming quantity of a thickening agent. For this purpose, a Wide variety of materials may be employed. These thickening or gelling agents may include any of the conventional metal salts or soaps, which are dispersed in the lubricating vehicle in grease-forming quantities, in such degree as to impart to the resulting grease composition, the desired consistency. Other thickening agents that may be employed in the grease formation may comprise the non-soap thickeners, such as surfaceamodified clays and silicas, aryl ureas, calcium complexes and similar materials. In general, grease thickeners may be employed which do not melt and dissolve when used at the required temperature within a particular environment; however, in all other respects any material which is normally employed for thickening or gelling hydrocarbon fluids for forming grease can be used in preparing the aforementioned improved grease in accordance with the present invention.

The metal salts of the salicylaldimine amide acids of the present invention, may be prepared, in general, by reacting salicylaldehyde and a diamine having the formula H NCH CH CH NHR, to obtain a salicylaldimine having the formula:

reacting the salicylaldimine thus formed with a member of the group consisting of maleic anhydride, succinic anhydride and tetr'apropenylsuccinic anhy'dride to obtain a salicylaldimine amide acid having the formula:

4 reacting the salicylaldimine amide acid thus formed with a material selected from the group consisting of metal hydroxides and metal alkoX-ides to form a metal salt of a salicylaldimine amide acid having the formula: 5

and wherein, in the aforementioned formulas, R is an alkyl group having from about 8 to about 18 carbon atoms, X is selected from the group consisting of CH:CH, CH CH and C H CHCH and M is a divalent metal. The aforementioned diamines, employed in producing the novel metal salts of the present invention, are commercially available under the trade name Duomeens, and are manufactured by Armour Industrial Chemical Company. Duomeen C, for example, has an average molecular weight of about 320, and Duomeen T has an average molecular weight of about 400. As the aforementioned structural formula indicates, the Duomeens contain both a primary and a secondary amine group.

More specifically, the novel metal salts of the present invention can be prepared by reacting one mole of salicylaldehyde with one mole of the aforementioned diamine, preferably at a temperature between about 100 C. and about 150 C. for 2 hours to form the corresponding salicylaldimine. This reaction is represented as follows:

CH0 HzNOHzCLhCI-IzNHR OH=NOH2CHZCH2NHR 1120 The salicylaldimine thus formed, is then stirred at a temperature of about C. for 2 hours with one mole of either maleic anhydride, succinic anhydride or tetrapropenylsuccinic anhydride to form the corresponding salicylaldimine acid. This reaction is represented as fol- The salicylaldimine amide acid thus formed is then heated at a temperature of from about C. to about 75 C. with either a metal hydroxide or a metal alkoxide Pereent N 9 Percent. Mg

to f orm the corresponding metal salt of the salicylaldimine amide acid. This reaction is represented as follows:

In each of. the aforementioned formulas of the reactions, as previously indicated, R is an alkyl group having. from about 8 to about 18 carbon atoms, X is selected from the group consisting of CHzCH, CH CH and l C H QCHCH and M is a divalent metal.

The following examples will serve to illustrate the preparation of the aforementioned novel metal salts of the. salicylaldimine amide acids of the present invention, and to demonstrate the eflectiveness thereof in organic compositions which are normally susceptible to deterioration by oxidation and corrosion, and particularly with reviously described, can be employed and will be readily apparent to those skilled in the art.

Example 1 61 grams;(0.5 mole). of salicylaldehyde were gradually added to 160 grams (0.5 mole) of Duomeen C diluted with 100 ccQof benzene, at room temperature with stirring; The reaction was exothermic, and the temperature rose .rapidlyto 65 C. At the completion of the addition; thexm ixture was refluxed at 150 C. to form 1 .therDuomeen C salicyl-aldimine and was held under refiux untiluwater stopped coming over. 1 was 10 cc., theory 9 cc.

Water collected To the above Duomeen C salicylaldimine were added 133. grams (0.5 mole) of r tetrapropenylsuccinic anhydride at room temperature with stirring. The reaction was again exothermic and the temperature rose rapidly to 55 C. The mixture was then stirred at. 95 C. for 2 hours to form the Duomeen C salicylaldimine tetrapropenylsuccinic amide acid. To the Duomeen C salicylaldirnine tetrapropenylsuccinic 11 amide acid. were added 21.6 grams (0.25 mole) of magnesium methoxide in methanol solution, obtained by reacting 6.08 grams (0.25 mole) of magnesium with 120 cc .of methanol. The mixture was gradually heated to 150* C. to distill out the methanol and benzene. The

final, product, the magnesium salt of Duomeen C salicylaldimine tetrapropenylsuocinic amide acid was clear and viscous at room temperature.

Estimated Found 1 WllZlLSO ccssof benzene, were gradually added at room temperature with stirring to 100 grams (0.25 mole) of Duomeen Tdiluted with195 grams of Process Oil #5.

, Themixture was refluxed at 150-155 C. to form the i Duomeen T salicylaldirnine and was held under reflux until water stopped coming over. Water collected was 5 -cc., theory 4.5 cc. To the above Duomeen T salicylaldimine were added 66.5 grams (0.25 mole) of tetrapropenylsuccinic anhydrideat room temperature with stirring. The reaction was exothermic and the temperature rose to C. rapidly. The mixture was stirred at 95 C. for 2 hours to form the Duomeen T salicylaldirnine tetrapropenylsuccinic amide acid. To the Duomeen T salicylaldimine tetrapropenylsuccinic amide acid were added 10.8 grams (0.125 mole) of magnesium methoxidein methanol solution, obtained by reacting 3.04 grams (0.125 mole) of magnesium with 60 cc. of methanol. The mixture was gradually heated to 150 C. to distill out the methanol and benzene. The product was filtered thnough. Hyfio clay. The final product, the magnesium salt of the Duomeen T salicylaldimine tetrapropenylsuccinic amide acid, which contained Process oil, was clear and fluid at room temperature.

30.5 grams (0.25 mole) of salicylaldehyde were gradually added at room temperature with stirring to 80 grams (0.25 mole) of Duomeen C diluted with 134 grams of xylene. The mixture was refluxed at 145 C. to form the Duomeen C salicylaldimine and was held under reflux at that temperature until water stopped coming over. Water collected was 5.5 cc., theory 4.5 cc. To the above Duomeen C salicylaldimine were added 25 grams (0.25 mole) of succinic anhydride at room temperature with stirring. The reaction was exothermic and the temperature rose to C. rapidly. The mixture was stirred at 95 C. for 2 hours to form the Duomeen C salicylaldirnine succinic amide acid. To the Duomeen C salicylaldimine succinic amide acid, were added at room temperature with stirring 10.8 grams (0.125 mole) of magnesium methoxide in methanol solution, obtained by reacting 3.04 grams (0.125 mole) of magnesium with cc. of methanol. The mixture was gradually heated to 130 C. and was held there until the methanol stopped coming over. The reaction product was filtered through Hyflo clay. The final product, the magnesium salt of Duomeen C salicylaldimine succinic amide acid, which contained 50% xylene was clear and fluid at room temperature.

30.5 grams (0.25 mole) of salicylaldehyde were gradually added to grams (0.25 mole) of Duomeen C diluted with 134 grams of xylene at room temperature with stirring. The mixture was refluxed at 145 C. to form the Duomeen C salicylaldimine and was held there until water stopped coming over. Water collected was 5.5 cc., theory 4.5 cc. To the above Duomeen C salicylaldimine were added 24.5 grams (0.25 mole) of maleic anhydri-de. The mixture was stirred at C. for 2 hours to form the Duomeen C salicylaldimine maleic amide acid. To the Duomeen C salicylaldimine maleic amide acid were added 10.8 grams (0.125 mole) of magnesium methoxide in methanol solution, obtained by reacting 3.04 grams (0.125 mole( of magnesium with 60 cc. of methanol. The mixture was gradually heated to C. :and was held there until. the methanol stopped coming over. The reaction product was filtered through Hyflo clay. The final product, the magnesium salt of Duomeen C salicylaldimine maleic amide acid, which contained 50% xylene, was clear and fluid at room temperature.

30.5 grams (0.25 mole) of salicylaldehyde, diluted with 60 cc. of benzene, were gradually added to 80 grams (0.25 mole) of Duomeen C, diluted with 209 grams of Process oil at room temperature with stirring. The mixture was gradually heated to reflux at 145 C. to form the Duomeen C salicylaldimine and was held there until water'stopped coming over; Watercoll'ected was cc., theory 4.5 cc. To the above Duomeen C salicylaldimine were added 66.5 grams (0.25 mole) of tetrapropenylsuccinic anhydride at room temperature with stirring. The mixture was gradually heated to 95 C. to form the Duomeen C tetrapropenylsuccinic amide acid and was held at 95 C. for 2 hours. To the Duomeen C tetrapropenylsuccinic amide acid were added at room temperature with stirring 17.2 grams (0.125 mole) of barium in the form of a barium methoxide solution. The mixture was gradually heated to 150 C. and was held there until the methanol and benzene stopped coming over. The product was filtered through Hyfio clay. The final product, the barium salt of Duomeen C tetrapropen-ylsuocinic amide acid, which contained 50% Process oil, was clear and fluid at room temperature.

30.5 grams (0.25 mole) of salicylaldehyde diluted with 60 cc. of benzene were gradually added at room temperature with stirring to 100 grams (0.25 mole) of Duomeen T diluted with 229 grams of Process oil. The mixture was gradually heated to reflux at 145 C. to form the Duomeen T salicylaldimine and was held there until water stopped coming over. Water collected was 5.5 cc, theory 4.5 cc. To the Duomeen T salicylaldimine were added 66.5 grams (0.25 mole) of tetrapropenylsuccinic anhydride at room temperature with stirring. The mixture was gradually heated to 95 C. with stirring to form the Duomeen T salicylaldimine tetraprop'enylsuccinic amide acid and was held there for 2 hours. To the Duomeen T salicylaldimine tetrapropenylsuccinic amide acid were added 17.2 grams (0.125 mole) of barium in the form of a barium methoxide solution. The mixture was gradually heated to 150 C. and was held there until the methanol and beneze stopped coming over. The product was filtered through Hyflo clay. The final product, the barium salt of Duomeen T salicylaldimine tetrapropenylsuccinic amide acid, which contained 50% Process oil, was clear and fluid at room temperature.

30.5 grams (0.25 mole) of salicyaldehyde, diluted with 60 cc. of benzene, were gradually added to 80 grams (0.25 mole) of Duomeen C, diluted with 177.5 grams of Process oil at room temperature with stirring. The mixture was gradually heated to reflux at 142 C. to form the Duomeen C salicylaldimine and was held there until water stopped coming over. Water collected was 5 cc., theory 4.5 cc. To the above Duomeen C sali-cyaldimine were added 66.5 grams (0.25 mole) of te-trapropenylsuccinic anhydride at room temperature with stirring. The mixture was gradually heated to C. with stirring to form the Duomeen C salicyaldimine tetrapropenylsuccinic amide acid and was held at 95 C. for 2 hours. To the Duomeen C salicylaldimine tetrapropenylsuccinic amide acid were added at room temperature with stirring 12.75 grams (0.125 mole) of calcium methoxide, obtained 'by reacting 5.75 grams (0.25 mole) of sodium in the form of a sodium methoxide solution with 15.4 grams (0.125 mole 10% excess) of calcium chloride dissolved in cc. of methanol. The mixture was gradually heated to C. and was held there until the methanol and" benzene stopped coming over. "The reaction product was filtered through Hyflo clay. The final product, the calcium salt of Duomeen C salicylaldimine tetrapropenylsuccinic amide acid, which contained 50% Process oil, was clear and fluid at room temperature.

30.5 grams (0.25 mole) of salicylaldehyde, diluted with 60 cc. of benzene, were gradually added at room temperature with stirring to 100 grams (0.25 mole) of Duomeen T, diluted with 197.5 grams of Process oil. The mixture was gradually heated to reflux at 142 C. to form the Duomeen T salicylaldimine and was held there until water stopped coming over. Water collected was 5.5 cc, theory 4.5 cc. To the above Duomeen T salicylaldimine were added 66.5 grams (0.25 mole) of tetrapropenylsuccinic anhydride at room temperature with stirring. The mixture was gradually heated to 95 C. to form the Duomeen T salicylaldimine tetrapropenylsuccinic amide acid and was held at 95 C. for 2 hours. To the above Duomeen T salicylaldimine tetrapropenylsuccinic amide acid were added at room temperature with stirring 12.75 grams (0.125 mole) of calcium methoxide, obtained by reacting 5.75 grams (0.25 mole) of sodium in the form of a sodium methoxide solution with 15.4 grams (0.125 mole 10% excess) of calcium chloride dissolved in 100 cc. of methanol. The mixture was gradually heated to C. and was held there until the methanol and benzene stopped coming over. The product was filtered through Hyflo clay. The final product, the calcium salt of Duomeen T salicylaldimine tetrapropenylsuccinic amide acid, which contained 50% Process oil, was clear and fluid at room temperature.

30.5 grams (0.25 mole) of salicylaldehyde, diluted with 60 cc. of benzene, were gradually added at room temperature with stirring to 80 grams (0.25 mole) of Duomeen C, diluted with grams of Process oil. The mixture was gradually heated to reflux at 145 C. :to form the Duomeen C salicylaldimine and was held under reflux until water stopped coming over. Water collected was 5 .5 cc., theory 4.5 cc. To the above Duomeen C salicylaldimine were added 66.5 grams (0.25 mole) of tetrapropenylsuccinic anhydride at room temeprature with stirring. The mixture was gradually heated to 95 C. to form the Duomeen C salicylaldimine tetrapropenylsuc- .100: cc. of methanol.

1 benzene stopped coming over.

cinic amide acid and was stirred at 95 C. for 2 hours.

To the above Duomeen C salicylaldimine tetrapropenylproduct, thBgZlI'lC salt of Duomeen C salicylaldimine tetrapropenylsuccinic amide acid, which contained 50% Process oil, was clear and fluid at room temperature.

Estimated Found Percent Zn 2. 30 2. 50 Percent N .e 1.95 1.97

Example 10 30.5 grams (0.25 mole) of salicylaldehyde, diluted with 60 ccrof benzene,. were gradually added at room 1 temperature with stirring to 100 grams of Duomeen T,

diluted with 200 grams of Processoil. The mixture was gradually. heated to reflux at 145 C. to form the DuomeeuT salicylaldimine and was held there until water stopped coming over. Water collected was cc., theory 4.5 cc... To the above Duomeen Tsa licylaldimine were added 66.5. grams (0.25 mole of tetra-propenylsuccinic anhydride at room temperature with stirring.

ture was gradually heated to 95 C. to form the Duomeen The mix- Tsalicylaldimine tetrapropenylsuccinic amide acid and was stirred at,i95" C. for 2 hours. To the Duomeen T (0.125 mole} 1% excess) of zinc chloride dissolved in The mixture as gradually heated to150". C.jand:was held there until the methanol and The product was filtered throughHyfio clay. The final product, the zinc salt of Duomeen salicylaldimine tetrapropenylsuccinic amide acid, which contained 50% Process oil, was clear and fluid .at .room temperature.

flux. :until water stopped coming over.

Estimated Found Percent Znq. 2.03 2. 25 Percent N 1 1. 75 2.18

Example 11 30.5 grams (0.25 mole) of salicylaldehyde, diluted withii60ocof benzene, were gradually added at room temperature with stirring to, 100 grams (0.25 mole) of Duomeen T diluted with 207 grams of Process oil.

. mixture was gradually heated to reflux at 142 C. to form The Du meen T lfsalicylaldimine tetrapropenylsuccinic amide yacidg and was held at 95 C. for 2 hours.

:meen .T salicylaldimine tetrapropenylsuccinic amide acid were added at room temperature with stirring 5.75 grams To the Duo- (-0.251 mole). of sodium in the" form of a sodium methoxidesolutionq The mixture was gradually heated to 150- C. to form a sodium salt. To the above sodium salt wereadded at room temperature with stirring 29.6 ,1 grams (0.1251mole+5% excess) of tin chloride dissolved in 150 cc. of methanol. The mixture was gradually heated to 150 C. to form the tin salt and was held at 150 C. until the methanol stopped coming over. The product was filtered through Hyfio clay. The final product, the tin salt of Duomeen T salicylaldimine tetrapropenylsuccinic amide acid, which contained 50 Process oil, was clear and fluid at room temperature.

Estimated Found Percent Sn 3. 55 3. Percent N 1. 69 1. 75

The anti-screen clogging characteristics of fuel oils, having incorporated therein the novel metal salts of the present invention, were determined from a standard screen clogging test. This test is conducted using a Sundstrant V3 or S1 home fuel oil burner pump with a selfcontained -mesh Monel metal screen. About 0.05 percent, by weight, of naturally-formed fuel oil sediment, composed of fuel oil, water, dirt, rust, and organic sludge is mixed with 10 liters of the fuel oil. This mixture is circulated by the pump through the screen for 6 hours. Then, the sludge deposit on the screen is washed olT with normal pentane and filtered through a tarred Gooch crucible. After drying, the material in the Gooch crucible is washed with a 50-50 (volume) acetone-methanol mixture. The total organic sediment is obtained by evaporating the pentane and the acetone-methanol filtrates. Drying and weighing the Gooch crucible yields the amount of inorganic sediment. The sum of the organic and inorganic deposits on the screen can be re ported in milligrams recovered or converted into percent screen clogging.

Example 12 The metal salts prepared in accordance with the foregoing Examples 1 through 11 were individually blended in test fuel oils comprising a blend of 60 percent distillate stock obtained from continuous catalytic cracking and 40 percent straight-run distillate stock, having a boiling range of between about 320 F. to about 640 F., and typical of No. 2 fuel oils. Each blend was subjected to the above-described screen clogging test. The test results obtained, are set forth in the following Table I:

In order to determine the sedimentation characteristics of fuel oils in which the novel metal salts of the present invention are incorporated, the 100 F. Fuel Oil Storage test, was employed. In this test a SOD-milliliter sample of the fuel oil under test is placed in a convected oven maintained at 100 F. for a period of 12 weeks. Thereafter, the sample is removed from the oven and cooled. The cooled sample is filtered through a tarred asbestos filter (Gooch crucible) to remove insoluble matter. The weight of such matter in milligrams is reported as the amount of sediment. A sample of the blank uninhibited oil is run along with a fuel oil blend under test. The effectiveness of a fuel oil containing an inhibitor is determined by comparing the weight of sediment formed in the inhibited oil with that formed in the uninhibited oil.

1 1 Example 13 The metal salts prepared in accordance with the foregoing Examples 1 through 11, were individually blended in test fuel oils similar to the aforementioned test fuel oils employed in the aforementioned screen clogging tests. The test results comparing the blended fuels, containing the novel metal salts of the present invention, and uninhibited fuels are set forth in Table II below:

TABLE IL-FUEL- OIL STORAGE TEST Inhibitors Conen., lb./ Sediment,

1,000 bbls. mgJliter Uninhibited fuel blend 6 Uninhibited fuel blend+Ex. 1- 10 4 Uninhibited fuel blend 0 0 Uninhibited fuel blend+Ex. 2. 25 4 Uninhibited fuel blend 0 6 Uninhibited fuel blend-l-Ex. 4- 10 4 Uniuhibited fuel blend 0 19 Uninhibited fuel blend+Ex. 5. l0 5 Uninhibited fuel blend 0 19 Uninhibited fuel blend+Ex. 6 25 4 Uninhibited fuel blend 0 19 Uninhibited fuel blend-l-Ex. 7 25 7 Uninhibited fuel blend 0 19 Uninhibited fuel blend+Ex. 8- 25 5 Uninhibited fuel blend 0 19 Uninhibited fuel blend-l-Ex. 9. 25 3 Uninhibited fuel blend 0 19 Uninhibited fuel blend 0 6 Uninhibited fuel blend+Ex. 25 5 Uninhibited fuel blend 0 19 Uninhibited fuel blend-l-Ex. 11 25 4 A similar storage test was performed withrespect to the metal salts prepared in accordance with the foregoing Examples 1 through 11, which were incorporated in a gasoline blend comprising 100 percent catalytically cracked component, and boiling within the range from approximately 100 F. to approximately 400 F., and containing 3 cc. of tetraethyl lead per gallon, as shown in Table III.

TABLE IIL-GASOLINE STORAGE TESTS Weeks Conan, ASTM Gum Inhibitors at 110 lb./1,000 Increase,

F. bbls. mg./100 ml.

Uninhib. gasoline3 cc. TEL/gal 16 0 15. 4 Uninhib. gasoline-3 cc.+Ex. 1 16 1. 4 Uninhib. gasoline- 16 0 15. 4 Uninhib. gasoline 16 5 1. 4 Uninhib. gasoline3 cc 16 O 15. 4 Uninhib. gasoline--23 co.+Ex. 4.. 16 10 0 Uninhib. gasoline-r3 cc 16 0 5.8 Uninhib. gas0line+3 cc. TEL/gal-.. 16 0 15. 4 Uninhib. gasoline-t3 cc.+Ex. 5 16 10 1. 4 Uninhib. gasoline- 16 0 5. 8 Uninhib. gasoline 16 10 0. 1 Uninhib. gasoline 16 0 5. 8 Uninhib. gasoline- 16 5 0. 9 Uninhib. gasoline- 16 0 5v 8 Uninhib. gasoline- 16 5 2. 4 Uninhib. gasoline- 16 0 5. 8 Uninhib. gasoline- 16 5 1. 6 Uninhib. gasoline- 16 0 5. 8 Uninhib. gasoline- 16 10 2. 5 Uninhib. gasoline- 16 0 5. 8 Uninhib. gaso1lne3 cc.+Ex. 11 16 10 0.5

It will be seen from Table III, above, that a marked decrease in ASTM gum content is observed with respect to the aforementioned gasoline blend containing the specified metal salts, as compared, in each instance, with the same gasoline blend, but not containing the metal salt additive.

Example 14 In order to test the anti-rust properties of fuel oils, ASTM Rust Test D66S, was employed and Was carried out for a period of 48 hours at 80 F., using distilled water, in which the inhibitors of Examples 1 through 11 were individually blended in test fuels comprising a blend of 60 percent distilled stock obtained from continuous catalytic cracking and 40 percent straight-run distilled stock having a boiling range between about 320 F. to about 640 F., and typical of No. 2 fuel oils. Each blend was subjected to the aforementioned ASTM Rust Test D-665, which is a dynamic test that indicates the ability to prevent rusting of ferrous metal surfaces in pipelines, tubes, etc. The test results obtained are set forth in the following Table IV:

TABLE IV.ASIM RUST TEST D-665 A similar ASTM rust test was prepared with respect to the aforementioned metal salt additives prepared in accordance with the foregoing Examples 1, 2, 5, 6 and 8, which were incorporated in a light turbine oil, comprising a furfural refined oil from Middle East crudes having a viscosity of about 150 Saybolt Seconds at F. The

test results comparing the blended turbine oil, containing the novel metal salts of the present invention, and the uninhibited turbine oil, are set forth in Table V below:

TABLE V.ASTM RUST TEST D-665 Inhibitors Concn., Wt. Rust Test Percent Result Blank light turbine oil 0 Fail.

Blank light turbine oil+Ex. 0.15 Pass.

Blanklight turbine oiH-Ex. O. 15 Do. Blank light turbine oil+Ex. 0. 20 Do. Blank light turbine oil+Ex. 0. 20 Do. Blank light turbine oil+Ex. 0.20 Do.

From the foregoing, it will be apparent that the additives of the present invention, comprising metal salts of salicylaldimine amide acids, are markedly effective in inhibiting clogging and deterioration of hydrocarbon compositions by corrosion, oxidation, and in inhibiting rusting of ferrous metal surfaces, and particularly with respect to the treatment of such hydrocarbons as petroleum distillate fuels. Furthermore, although the present invention has been described with preferred embodiments, it will be understood that modifications and adaptations thereof, which will be obvious to those skilled in the art, may be resorted to without departing from the spirit and scope of the invention.

We claim:

1. Organic compositions normally susceptible to deterioration, containing a small amount, to inhibit said deterioration, of a metal salt of a salicylaldimine amide acid, having the formula:

wherein X is selected from the group consisting of CHzCH, CH CH and C H CHCH R is an alkyl group having from about 8 to about 18 carbon atoms and M is a divalent metal.

2. A composition in accordance with claim 1 wherein said metal salt is present in an amount from about .001 to 2112011111110 percent, by weight, of the total of said composition.

3. A composition in accordance with claim 1 wherein said metal salt is present in an amount from about .001 to about .01 percent, by Weight, of the total of said composition.

4. A; composition in accordance with claim 1 wherein said metal salt is present in an amount from about 0.1 to about 5 percent, by weight, of the total of said composition.

5.13 A composition in accordance with claim 1 wherein said composition is a liquid hydrocarbon comprising a .petroleum distillate fuel oil having an initial boiling point: from :about 75 F. to about 135 F. and an end boilinglpoint from about 250 F. to about 750 F.

6.1iA -composition in accordance with claim 1 wherein said composition comprises a lubricant.

7.A composition in accordance with claim 1 wherein said composition comprises a grease.

SAThe composition of claim 5 wherein said liquid hydrocarbon comprises a gasoline.

9. The composition of claim 5 wherein said liquid hydrocarbon comprises a jet fuel.

The composition of claim 5 wherein said liquid hydrocarbon comprises a turbine fuel.

llillA metal salt of a salicylaldimine amide acid hav-- ing the formula:

(Tr-O 0 wherein X is selected from the group consisting of group having from about 8. to about 18 carbon atoms 14 H NCH CH CH NHR, to obtain a salicylaldimine having the formula:

reacting the salicylaldimine thus formed with a member of the group consisting of maleic anhydride, suc cinic anhydride and tetrapropenylsuccinic anhydride to obtain a salicylaldimine amide acid having the formula:

OH ll CNRCH2CH2CHzN: -=CH l ll reacting the salicylaldimine amide acid thus formed with a material selected from the group consisting of metal hydroxides and metal alkoxides to form a metal salt of a salicylaldimine amide acid having the formula:

and wherein, in the aforementioned formulas, R is an alkyl group having from about 8 to about 18 carbon atoms, X is selected from the group consisting of CHzCH, CH CH and C H CHCH and M is a divalent metal.

References Cited by the Examiner UNITED STATES PATENTS 2,458,425 1/ 1949 R-occhini -2 25'233.6 2,458,527 1/1949 Oberright 252-33.6 2,699,427 1/1955 Smith et al. 25233.6

FOREIGN PATENTS 598,944 5/ 1960 Canada.

DANIEL E. WYMAN, Primary Examiner.

C. F. DEES, Assistant Examiner. 

1. ORGANIC COMPOSITIONS NORMALLY SUSCEPTIBLE TO DETERIORATION, CONTAINING A SMALL AMOUNT, TO INHIBIT SAID DETERIORATION, OF A METAL SALT OF A SALICYLALDMINE AMIDE ACID, HAVING THE FORMULA:
 6. A COMPOSITION IN ACCORDANCE WITH 1 WHEREIN SAID COMPOSITION COMPRISES A LUBRICANT. 